TWI670381B - Copper heat releasing material, printed wiring board, manufacturing method thereof, and product using the copper heat releasing material - Google Patents

Abstract

The invention provides a copper heat-radiating material with good heat-releasing properties. The copper heat-generating material of the present invention forms an alloy layer containing one or more metals selected from Cu, Co, Ni, W, P, Zn, Cr, Fe, Sn, and Mo on one or both sides, and uses a lightning The surface roughness Sz of one or both surfaces measured by a laser microscope with an emission wavelength of 405 nm is 5 μm or more.

Description

Copper heat radiating material, printed wiring board and manufacturing method thereof, and products using the copper heat radiating material

The present invention relates to a method for manufacturing a copper heat-radiating material, a copper foil with a carrier, a terminal, a laminated body, a shielding material, a printed wiring board, a metal processing member, an electronic device, and a printed wiring board.

In recent years, with the miniaturization and high definition of electronic equipment, failures caused by heat generation of electronic components used have become problems. In particular, among the electronic parts used in electric cars or hybrid electric cars that have grown significantly, parts having a significantly high current, such as a connector having a battery section, generate heat when the electric parts are energized. In addition, a heat sink plate called a liquid crystal frame is used as an input plate of a smartphone or a liquid crystal of a tablet computer. The heat sink dissipates heat from the surrounding liquid crystal parts, IC chips, and the like to the outside, and suppresses malfunctions of the electronic parts.

Patent Document 1: Japanese Patent Application Publication No. 07-094644

Patent Document 2: Japanese Patent Application Laid-Open No. 08-078461

However, as mentioned above, due to the changes in electronic equipment in recent years, It cannot satisfy the function of not dissipating the heat from the liquid crystal parts, IC chips, etc. due to thermal conduction, radiant heat, convection heat, etc., to the outside and dissipating well.

Therefore, an object of the present invention is to provide a copper heat-radiating material having good heat-releasing properties.

The inventor has repeatedly studied intensively, and as a result, it has been found that, by forming an alloy layer containing a specific metal on the surface and controlling the surface to a specific surface roughness Sz, a copper heat radiating material having good heat release properties can be provided.

The present invention, which is based on the above findings, is, in one aspect, a copper heat radiating material formed on one or both sides containing a material selected from the group consisting of Cu, Co, Ni, W, P, Zn, Cr, Fe, and Sn. And Mo, an alloy layer of one or more metals, and the surface roughness Sz of one or both of the surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 5 μm or more.

In one embodiment of the copper heat-emitting material of the present invention, the surface roughness Sz of one or both of the surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 7 μm or more.

In another embodiment, the copper heat-generating material of the present invention has a surface roughness Sz of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm, which is 10 μm or more.

In another embodiment, the copper heat radiating material of the present invention has a surface roughness Sz of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm and is 14 μm or more.

In another embodiment, the copper heat radiating material of the present invention has a surface roughness Sz of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm, which is 90 μm or less.

In another embodiment, the copper heat radiation material of the present invention uses the wavelength of laser light. The surface roughness Sa of one or both of the surfaces measured by a laser microscope of 405 nm is 0.13 μm or more.

In another embodiment, the copper heat radiating material of the present invention has a surface roughness Sku of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm, which is 6 or more.

In another embodiment, the copper heat-generating material of the present invention sets the surface area of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm to A, and sets the area in plan view to B. The surface area ratio A / B is 1.35 or more.

In other embodiments, the copper heat-radiating material of the present invention has a color difference ΔL based on JISZ8730 on one or both surfaces satisfying ΔL ≦ −35.

In another embodiment, the copper heat radiation material of the present invention has a color difference Δa based on JISZ8730 on one or both surfaces satisfying Δa ≦ 15.

In another embodiment, the copper heat radiating material of the present invention has a color difference Δb based on JISZ8730 on one or both surfaces satisfying Δb ≦ 17.

In other embodiments, the copper heat radiating material of the present invention has an emissivity of 0.092 or more on one or both surfaces.

In another embodiment, the copper heat radiation material of the present invention includes a resin layer on one or both surfaces.

In another embodiment, the copper heat radiating material of the present invention is such that the resin layer contains a dielectric.

In other aspects, the present invention is a copper foil with a carrier, which has an intermediate layer and an ultra-thin copper layer sequentially on one or both sides of the carrier, and the ultra-thin copper layer is the copper heat-emitting material of the present invention.

In one embodiment, the copper foil with a carrier of the present invention has the intermediate layer, the ultra-thin copper layer in this order on one side of the carrier, and a roughened layer on the other side of the carrier.

The invention is, in other aspects, a connector that uses the copper heat sink of the invention.

The present invention is, in other aspects, a terminal that uses the copper heat sink of the present invention.

The present invention is, in other aspects, a laminated body manufactured in the following manner: The copper heat-generating material of the present invention or the copper foil with a carrier of the present invention, any adhesive layer or adhesive layer, and a resin are sequentially laminated. A substrate or a substrate or a case or a metal working member or an electronic part or an electronic machine or a liquid crystal panel or a display or a partition.

In another aspect, the present invention is a shielding material provided with the laminated body of the present invention.

In another aspect, the present invention is a printed wiring board including the laminated body of the present invention.

In another aspect, the present invention is a metal-processed member using the copper heat-radiating material of the present invention or the copper foil with a carrier of the present invention.

The present invention is, in other aspects, an electronic device using the copper heat radiating material of the present invention or the copper foil with a carrier of the present invention.

The present invention is, in other aspects, a method for manufacturing a printed wiring board, which includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After the carrier copper foil and the insulating substrate are laminated, the copper foil with the carrier is peeled off. The step of the carrier forms a metal-clad laminate, and then a circuit is formed by any one of a semi-additive method, a subtractive method, a partial additive method, or an improved semi-additive method.

The present invention is, in other aspects, a method for manufacturing a printed wiring board, which includes the following steps: forming a circuit on the surface of the ultra-thin copper layer or the surface of the carrier side of the copper foil with a carrier of the present invention; Method of forming a resin layer on the ultra-thin copper layer side surface of the copper foil with a carrier or the carrier side surface; forming a circuit on the resin layer; after forming a circuit on the resin layer, peeling off the carrier or the ultra-thin layer A copper layer; and a circuit formed on the surface of the ultra-thin copper layer or the surface of the carrier by burying the resin layer by removing the ultra-thin copper layer or the carrier after peeling off the carrier or the ultra-thin copper layer Exposed.

According to the present invention, it is possible to provide a copper heat radiation material having good heat radiation properties.

d1‧‧‧vertical

d2‧‧‧vertical

w1‧‧‧horizontal

w2‧‧‧horizontal

Figure 1 is a schematic diagram of the upper surface of the sample of the embodiment.

Fig. 2 is a schematic sectional view of a sample of the embodiment.

[Form and manufacturing method of copper exothermic material]

As the copper heat radiation material used in the present invention, copper or a copper alloy can be used.

Typical examples of copper include phosphorus deoxidized copper (JIS H 3100 alloy numbers C1201, C1220, and C1221), oxygen-free copper (JIS H3100 alloy number C1020), and refined copper (JIS H3100) as specified in JIS H0500 and JIS H3100. Alloy No. C1100), electrolytic copper foil and the like having a purity of 95% by mass or more, and more preferably 99.90% by mass or more of copper. It can also be set to contain copper or copper containing one or more of Sn, Ag, Au, Co, Cr, Fe, In, Ni, P, Si, Te, Ti, Zn, B, Mn, and Zr in a total amount of 0.001 to 4.0% by mass. Copper alloy.

Examples of the copper alloy include phosphor bronze, Carson alloy, red brass, brass, white copper, and other copper alloys. In addition, as copper or a copper alloy in the present invention, those specified in JIS H 3100 to JIS H3510, JIS H 5120, JIS H 5121, JIS C 2520 to JIS C 2801, and JIS E 2101 to JIS E 2102 can also be used. In addition, as long as there is no special negation in this specification, the JIS standard listed for metal specification means the JIS standard of 2001 edition.

Regarding phosphor bronze, typically, phosphor bronze refers to a copper alloy containing copper as a main component and containing Sn and P having a mass less than Sn. As an example, phosphor bronze has a composition including 3.5 to 11% by mass of Sn and 0.03 to 0.35% by mass of P, and the remainder is composed of copper and unavoidable impurities. Phosphor bronze may also contain elements such as Ni and Zn in a total amount of 1.0% by mass or less.

The Carson alloy typically refers to a copper alloy that is added with an element that forms a compound with Si (for example, any one or more of Ni, Co, and Cr) and precipitates as second-phase particles in the mother phase. As an example, the Carson alloy has a composition containing any one or more of Ni, Co, and Cr in an amount of 0.5 to 4.0% by mass, and Si in an amount of 0.1 to 1.3% by mass, and the remainder is composed of copper and unavoidable impurities. As another example, the Carson alloy has a composition containing at least one of Ni and Co in a total of 0.5 to 4.0% by mass, Si in a range of 0.1 to 1.3% by mass, and Cr in a range of 0.03 to 0.5% by mass. The remainder consists of copper and unavoidable impurities. Furthermore, as another example, the Carson alloy has the following composition: containing 0.5 to 4.0% by mass of Ni, 0.1 to 1.3% by mass of Si, and 0.5 to 2.5% by mass of Co, and the remaining portion is composed of copper and unavoidable impurities. As another example, Carson alloy has the following composition: containing 0.5 to 4.0% by mass of Ni, 0.1 to 1.3% by mass of Si, 0.5 to 2.5% by mass of Co, and 0.03 to 0.5% by mass of Cr, and the remainder is made of copper and Inevitable impurity formation. Furthermore, as another example, the Carson alloy has a composition containing 0.2 to 1.3% by mass of Si and 0.5 to 2.5% by mass of Co, and the remainder is composed of copper and unavoidable impurities. Other elements (such as Mg, Sn, B, Ti, Mn, Ag, P, Zn, As, Sb, Be, Zr, Al, and Fe) can be arbitrarily added to the Carson alloy. Generally, these other elements are added to a total of about 5.0% by mass. For example, as another example, the Carson alloy has a composition including any one or more of Ni, Co, and Cr in a total amount of 0.5 to 4.0% by mass, Si in a range of 0.1 to 1.3% by mass, Sn in a range of 0.01 to 2.0% by mass, and 0.01 to 2.0% by mass. 2.0% by mass of Zn, and the remainder is made of copper and unavoidable impurities.

In the present invention, red brass refers to an alloy of copper and zinc, and a copper alloy containing 1 to 20% by mass of zinc, and more preferably 1 to 10% by mass of zinc. The red brass may contain tin in an amount of 0.1 to 1.0% by mass.

In the present invention, brass refers to an alloy of copper and zinc, and especially a copper alloy containing 20% by mass or more of zinc. The upper limit of zinc is not particularly limited, but is 60% by mass or less, preferably 45% by mass or less, or 40% by mass or less.

In the present invention, white copper refers to a copper alloy containing copper as a main component and containing 60 to 75% by mass of copper, 8.5% to 19.5% by mass nickel, and 10 to 30% by mass zinc.

In the present invention, other copper alloys are those containing a total of 8.0% by mass or less. One or two or more of Zn, Sn, Ni, Mg, Fe, Si, P, Co, Mn, Zr, Ag, B, Cr, and Ti. The remaining portion is a copper alloy composed of unavoidable impurities and copper.

Furthermore, metals with good thermal conductivity such as aluminum or aluminum alloys, nickel, nickel alloys, magnesium, magnesium alloys, silver, silver alloys, gold, gold alloys, precious metals, alloys containing precious metals, etc. may be used in place of the present invention. It is made of copper or copper alloy of copper heat radiating material. In addition, the thermal conductivity of the metal used for the copper heat radiation material and the heat radiation material is preferably 32 W / (m · K) or more.

The shape of the copper heat-radiating material used in the present invention is not particularly limited, and it can be processed into the final shape of the electronic component, or it can be partially pressed. It is not necessary to perform shape processing, but it can be a sheet, plate, strip, foil, rod, line, box, or three-dimensional shape (cuboid, cube, polyhedron, triangular cone, cylinder, cylinder, cone, ball, three-dimensional with unevenness, Plane and / or curved solid). The copper heat-emitting material is preferably a rolled copper foil or an electrolytic copper foil, and more preferably a rolled copper foil. The "copper foil" includes a copper alloy foil.

The thickness of the copper heat-radiating material is not particularly limited. For example, the thickness can be adjusted to a suitable thickness according to the application and used. For example, it can be set to about 1 to 5000 μm or about 2 to 1000 μm. Especially when it is used for forming a circuit, it can be set to 35 μm or less. When a shield tape is used as a shield material, it can be set to be thinner than 18 μm. In the case of being used as a shield material, a terminal, a shell, etc. other than a connector, a shielding tape inside an electronic device, it can also be applied to a material having a thickness of 70 to 1000 μm, and the upper limit thickness is not particularly specified. In addition, the shielding material may be used solely for shielding purposes, or it may be a shielding part that is configured to be used together with other parts for shielding purposes.

The surface roughness Sz (the maximum height of the surface) of one or both of the surfaces measured by the laser microscope with a laser light wavelength of 405 nm of the copper exothermic material of the present invention is 5 μm or more. If the surface roughness Sz of one or both surfaces of the copper exothermic material is less than 5 μm, The heat exothermicity of the hot body becomes poor. The surface roughness Sz of one or both surfaces of the copper heat-radiating material is preferably 7 μm or more, more preferably 10 μm or more, even more preferably 14 μm or more, still more preferably 15 μm or more, and even more preferably 25 μm or more. The upper limit is not particularly limited, and may be, for example, 90 μm or less, 80 μm or less, or 70 μm or less. When surface roughness Sz exceeds 90 micrometers, productivity may fall.

Here, the "surface" of the copper heat-radiating material basically means the surface of the alloy layer of the copper heat-radiating material. On the surface of the copper heat-radiating material, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling The case of a surface treatment layer such as a treatment layer means the outermost surface after the surface treatment layer is provided.

The surface roughness Sa (arithmetic average surface roughness) of one or both surfaces of the copper heat radiation material of the present invention is preferably 0.13 μm or more. If the surface roughness Sa of one or both surfaces of the copper heat radiating material is less than 0.13 μm, there is a concern that the heat radiating property of the heat from the heating element is reduced. The surface roughness Sa of one or both surfaces of the copper heat-radiating material is more preferably 0.20 μm or more, even more preferably 0.25 μm or more, and even more preferably 0.30 μm or more, typically 0.1 to 1.0 μm, and more typically It is 0.1 to 0.9 μm.

The Sku (the sharpness and kurtosis of the surface height distribution) of one or both surfaces of the copper heat radiating material of the present invention is preferably 6 or more. If the Sku of one or both surfaces of the copper exothermic material is less than 6, there is a concern that the exothermic property of the heat from the heating element is reduced. The Sku of one or both surfaces of the copper heat-radiating material is more preferably 9 or more, further preferably 10 or more, further preferably 40 or more, and even more preferably 60 or more, typically 3 to 200, and more typically It is 4 ~ 180.

Regarding the copper heat-emitting material of the present invention, the surface area of one or both of the surfaces measured by a laser microscope with a laser light wavelength of 405 nm is set to A, and the surface area ratio A / B when the area in plan view is set to B is Above 1.35. If the surface area ratio of one or two surfaces is A / B If it is less than 1.35, there is a concern that the heat release property of the heat from the heating element is reduced. The surface area ratio is more than 1.36, more preferably 1.38 or more, even more preferably 1.40 or more, even more preferably 1.45 or more, typically 1.00 to 8.00, and more typically 1.10 to 7.50. .

The emissivity of one or both surfaces of the copper heat radiating material of the present invention is preferably 0.092 or more. If the emissivity of one or both surfaces of the copper heat radiating material is 0.092 or more, the heat from the heating element can be radiated well. The emissivity of one or both surfaces of the copper heat-radiating material is more preferably 0.10 or more, even more preferably 0.123 or more, even more preferably 0.154 or more, even more preferably 0.185 or more, and even more preferably 0.246 or more.

The emissivity of one or both surfaces of the copper heat-radiating material of the present invention does not need to specify an upper limit, typically 1 or less, more typically 0.99 or less, more typically 0.95 or less, and more typically 0.90 or less, more typically 0.85 or less, and more typically 0.80 or less. In addition, if the emissivity of one or both surfaces of the copper heat radiating material is 0.90 or less, the manufacturability is improved.

Regarding the copper heat-generating material of the present invention, it is preferable to use a white plate with one or two surfaces (when the light source is set to D65 and the field of view is 10 degrees, the X ₁₀ Y ₁₀ Z ₁₀ color system of the white plate (JIS Z8701 1999 The three stimulus values are X ₁₀ = 80.7, Y ₁₀ = 85.6, Z ₁₀ = 91.5, and the object color of the white board in the L ^* a ^* b ^* color system is L ^* = 94.14, a ^* = -0.90 , b ^* = 0.24) when the color of the object color and the reference color is set based on the CIE lightness two L ^* a ^* b ^* color system stipulated JISZ8730 the color difference △ L (JIS Z8729 (2004) in the color of the object L ^* Difference) satisfies ΔL ≦ -35. In this way, if the color difference ΔL on the surface of the copper exothermic material satisfies ΔL ≦ -35, the heat, radiant heat, and convective heat caused by the thermal conduction absorbed from the heating element can be well absorbed and exothermic. The surface color difference △ L is more preferably △ L ≦ -40, further more preferably △ L ≦ -45, even more preferably △ L ≦ -50, even more preferably △ L ≦ -60, and even more preferably △ L ≦ -70, typically -90 ≦ △ L ≦ -5, -90 ≦ △ L ≦ -10, -88 ≦ △ L ≦ -35, or -85 ≦ △ L ≦ -35.

Regarding the copper heat-generating material of the present invention, it is preferable to use a white plate with one or two surfaces (when the light source is set to D65 and the field of view is 10 degrees, the X ₁₀ Y ₁₀ Z ₁₀ color system of the white plate (JIS Z8701 1999 The three stimulus values are X ₁₀ = 80.7, Y ₁₀ = 85.6, and Z ₁₀ = 91.5, and the object color of the white plate in the L ^* a ^* b ^* color system is L ^* = 94.14, a ^* =-0.90 , b ^* = 0.24) when the color of the object color as a reference color based on JISZ8730 and the color difference △ a (JIS Z8729 (2004) of a predetermined two L ^* a ^* b ^* color system, the color of the object color coordinates a ^* Difference) satisfies Δa ≦ 15. In this way, if the color difference Δa on the surface of the copper heat-emitting material satisfies Δa ≦ 15, the heat, radiant heat, convection heat, and the like caused by the heat conduction absorbed from the heating element can be well absorbed. The surface color difference Δa is more preferably △ a ≦ 10, further more preferably △ a ≦ 5, even more preferably △ a ≦ 4, typically -10 ≦ △ a ≦ 15, and more typically -8 ≦ △ a ≦ 15.

Regarding the copper heat-generating material of the present invention, it is preferable to use a white plate with one or two surfaces (when the light source is set to D65 and the field of view is 10 degrees, the X ₁₀ Y ₁₀ Z ₁₀ color system of the white plate (JIS Z8701 1999 The three stimulus values are X ₁₀ = 80.7, Y ₁₀ = 85.6, Z ₁₀ = 91.5, and the object color of the white board in the L ^* a ^* b ^* color system is L ^* = 94.14, a ^* = -0.90 , b ^* = 0.24) is set to the color of the object color and the reference color based upon the color of JISZ8730 △ b (JIS Z8729 (2004) prescribed the L ^* a ^* b ^* color system of table two object colors of the color coordinate b ^* Difference) satisfies Δb ≦ 17. In this way, if the color difference Δb on the surface of the copper heat-emitting material satisfies Δb ≦ 17, the heat, radiant heat, convection heat, and the like caused by the thermal conduction absorbed from the heating element can be well absorbed. The surface color difference △ b is more preferably △ b ≦ 15, further more preferably △ b ≦ 5, even more preferably △ b ≦ 3, typically -15 ≦ △ b ≦ 17, and more typically -10 ≦ Δb ≦ 17.

Regarding the copper heat-generating material of the present invention, it is preferable to use a white plate with one or two surfaces (when the light source is set to D65 and the field of view is 10 degrees, the X ₁₀ Y ₁₀ Z ₁₀ color system of the white plate (JIS Z8701 1999 The three stimulus values are X ₁₀ = 80.7, Y ₁₀ = 85.6, and Z ₁₀ = 91.5, and the object color of the white plate in the L ^* a ^* b ^* color system is L ^* = 94.14, a ^* =-0.90 (, B ^* = 0.24) The color difference when the object color is set as the reference color and the color difference ΔE ^* ab based on JISZ8730 satisfies 47 ≦ ΔE ^* ab. In this way, if the color difference ΔE ^* ab on the surface of the copper heat-emitting material satisfies 47 ≦ ΔE ^* ab, the heat, radiant heat, and convection heat caused by the thermal conduction absorbed from the heating element can be well absorbed. The surface color difference ΔE ^* ab is more preferably 50 ≦ △ E ^* ab, further more preferably 55 ≦ △ E ^* ab, even more preferably 60 ≦ △ E ^* ab, and even more preferably 71 ≦ △ E ^* ab, Typically, 47 ≦ △ E ^* ab ≦ 90, more typically 47 ≦ △ E ^* ab ≦ 88, and more typically 47 ≦ △ E ^* ab ≦ 85.

Here, the above-mentioned color differences ΔL, Δa, and Δb are measured using a color difference meter, respectively, taking black / white / red / green / yellow / blue, and using L ^* a ^* b ^* based on JIS Z8730 (2009). A comprehensive index expressed systematically, and expressed as △ L: white and black, △ a: red and green, and △ b: yellow and blue. In addition, ΔE ^* ab is expressed by the following formula using these color differences. This color difference (ΔL, Δa, Δb) can be measured using a color difference meter MiniScan XE Plus manufactured by HunterLab.

The copper heat radiating material of the present invention forms an alloy layer containing one or more metals selected from Cu, Co, Ni, W, P, Zn, Cr, Fe, Sn, and Mo on one or both sides. With this configuration, the above-mentioned chromatic aberration and surface roughness can be adjusted, and the heat, radiant heat, and convective heat caused by thermal conduction absorbed from the heating element can be well absorbed by adjusting the chromatic aberration. Furthermore, the alloy layer may be formed by wet plating such as electroplating, electroless plating, and dip plating, or by sputtering, CVD, It is formed by PDV-like dry plating. From the viewpoint of cost, electroplating is preferred.

The alloy layer of the copper heat-generating material of the present invention can be formed, for example, by using the following plating conditions alone or in combination, and further controlling the number of treatments. It should be noted that the remainder of the treatment liquid used in the present invention, such as slag removal treatment, electrolysis, surface treatment, or plating, is water unless specifically stated otherwise.

(Alloy layer formation plating conditions 1: Cu layer)

‧Plating solution composition: Cu concentration 5 ~ 20g / L

‧PH value: 1.0 ~ 5.0

‧Temperature: 25 ~ 55 ℃

‧Current density: 2 ~ 70A / dm ²

‧Plating time: 0.2 ~ 20 seconds

(Plating conditions for alloy layer formation 2: Cu-Co-Ni layer)

‧Plating solution composition: Cu concentration 10 ~ 20g / L, Co concentration 5 ~ 10g / L, Ni concentration 5 ~ 10g / L

‧PH value: 2.0 ~ 6.0

‧Temperature: 25 ~ 55 ℃

‧Current density: 10 ~ 60A / dm ²

‧Plating time: 0.3 ~ 10 seconds

(Plating conditions for alloy layer formation 3: Cu-Co-Ni-P layer)

‧Plating composition: Cu concentration 10 ~ 20g / L, Co concentration 5 ~ 10g / L, Ni concentration 5 ~ 10g / L, P concentration 10 ~ 800mg / L

‧PH value: 2.0 ~ 6.0

‧Temperature: 25 ~ 55 ℃

‧Current density: 10 ~ 60A / dm ²

‧Plating time: 0.3 ~ 10 seconds

(Plating conditions for alloy layer formation 4: Ni-Zn layer)

‧Plating composition: Ni concentration 10 ~ 60g / L, Zn concentration 5 ~ 30g / L

‧PH value: 3.5 ~ 6.0

‧Temperature: 25 ~ 55 ℃

‧Current density: 0.2 ~ 3.0A / dm ²

‧Plating time: 4 ~ 181 seconds

(Plating conditions for alloy layer formation 5: Cu-Ni-P layer)

‧Plating composition: Cu concentration 5 ~ 15g / L, Ni concentration 10 ~ 30g / L, P concentration 10 ~ 800mg / L

‧PH value: 2.0 ~ 5.0

‧Temperature: 25 ~ 55 ℃

‧Current density: 10 ~ 60A / dm ²

‧Plating time: 0.2 ~ 10 seconds

In the case where the alloy layer is formed by the above-mentioned alloy layer forming plating conditions 1 to 3 and 5, it is necessary to divide the surface treatment into multiple times.

(Plating conditions for alloy layer formation 6: Cr-Zn layer)

‧Plating composition: Cr concentration 2 ~ 8g / L, Zn concentration 0.1 ~ 1.0g / L

‧PH value: 2.0 ~ 4.0

‧Temperature: 40 ~ 60 ℃

‧Current density: 0.5 ~ 3.0A / dm ²

‧Plating time: 0.2 ~ 10 seconds

(Alloy layer formation plating conditions 7: Cu-Ni-W layer)

‧Plating composition: Cu concentration 5 ~ 15g / L, Ni concentration 10 ~ 40g / L, W concentration 10 ~ 1000mg / L

‧PH value: 2.0 ~ 4.0

‧Temperature: 40 ~ 60 ℃

‧Current density: 10 ~ 60A / dm ²

‧Plating time: 0.2 ~ 10 seconds

(Alloy layer formation plating conditions 8: Ni-W-Sn layer)

‧Plating composition: Ni concentration 10 ~ 50g / L, W concentration 300 ~ 3000mg / L, Sn concentration 100 ~ 1000mg / L

‧PH value: 3.0 ~ 6.5

‧Temperature: 40 ~ 60 ℃

‧Current density: 0.1 ~ 4.0A / dm ²

‧Plating time: 10 ~ 60 seconds

(Alloy layer forming plating conditions 7: Cu-Ni-Mo-Fe layer)

‧Plating composition: Cu concentration 5 ~ 15g / L, Ni concentration 10 ~ 40g / L, Mo concentration 50 ~ 5000mg / L, Fe concentration 0.5 ~ 5.0g / L

‧PH value: 2.0 ~ 5.0

‧Temperature: 40 ~ 60 ℃

‧Current density: 10 ~ 60A / dm ²

‧Plating time: 5 ~ 30 seconds

Moreover, a well-known additive can also be used for the plating liquid which forms an alloy layer. As the additive, for example, an additive that promotes precipitation of metal ions, an additive that stabilizes the presence of metal ions in the plating agent, an additive that uniformly precipitates metal ions, a leveling agent, and a glossing agent can also be used.

For example, chlorine, bis (3-sulfopropyl) disulfide, amine compounds, gelatin, cellulose, ethylene glycol, thiourea, sulfides, organic sulfur compounds, and the like may be used as additives. The concentration of the additives may be a concentration that is generally used. By adding this additive, the hue and unevenness of the surface can be controlled.

When the above alloy layer is used, the total adhesion amount of one or more metals selected from the group consisting of Co, Ni, W, P, Zn, Cr, Fe, Sn, and Mo is preferably 0.1 to 100,000 μg / dm. ² , preferably 5 to 80,000 μg / dm ² , preferably 10 to 85,000 μg / dm ² , and preferably 100 to 80,000 μg / dm ² . When it is less than 0.1 μg / dm ² , the effect of providing the alloy layer may be reduced in some cases. Moreover, when it exceeds 100,000 microgram / dm <^2> , productivity may fall. In addition, when the circuit is formed on a copper heat-dissipating material, and the circuit is used to transmit high-frequency signals, the upper limit of the adhesion amount of Ni contained in the alloy layer is preferably 4000 μg / dm ² or less, and more preferably 3000 μg / dm ² or less, more preferably 1400 μg / dm ² or less, and more preferably 1000 μg / dm ² or less. The lower limit of the adhesion amount of Ni is typically 50 μg / dm ² or more, more preferably 100 μg / dm ² , and more preferably 300 μg / dm ² or more. That is, the Ni deposition amount is typically contained in the alloy layer in terms of 50μg / dm ² or more and 4000μg / dm ² or less.

In addition, when the circuit is formed on a copper heat-radiating material and the circuit is used to transmit high-frequency signals, the upper limits of the adhesion amounts of Co, Fe, and Mo contained in the alloy layer are preferably 6000 μg / dm ^{2 respectively.} or less, more preferably 5000μg / dm ² or less, more preferably 3000μg / dm ² or less, more preferably 2400μg / dm ² or less, more preferably set to 2000μg / dm ² or less. The lower limit of the adhesion amount of Co is typically 50 μg / dm ² or more, more preferably 100 μg / dm ² , and more preferably 300 μg / dm ² or more. That is, a typical deposition amount of Co included in the alloy layer in terms of 50μg / dm ² or more and 6000μg / dm ² or less. In addition, when the alloy layer includes a layer containing Co and / or Ni in addition to the Cu-Co-Ni alloy plating layer, the total adhesion amount of Ni and the deposition amount of Co in the entire alloy layer may be set as described above. range.

When the above alloy layer contains Cu, there is no need to specifically set an upper limit thereof, typically 100 mg / dm ² or less, more typically 90 mg / dm ² or less, and more typically 80 mg / dm ² or less. When the above-mentioned alloy layer contains Cu, there is no need to specifically set the lower limit, which is typically 0.01 μg / dm ² or more, more typically 0.1 μg / dm ² or more, and more typically 1 μg / dm. ² or more, typically 0.01 μg / dm ² or more and 100 mg / dm ² or less.

In addition, a surface treatment layer may be provided on the surface of copper or copper alloy or the surface of the alloy layer used for the copper heat-emitting material. The surface treatment layer may be a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, a silane coupling treatment layer, and a plating layer. The surface treatment layer can be formed by forming a black resin on the surface of the copper heat-emitting material. The black resin can be formed by, for example, impregnating a black paint with an epoxy resin, applying only a specific thickness, and drying.

<Surface treatment layer>

The surface of the copper or copper alloy or the surface of the alloy layer used for the copper heat-generating material may be provided with a roughening treatment layer by performing a roughening treatment, for example, to improve the adhesion with the adhesive layer. . The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughened layer may be a layer composed of any elementary substance selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing any one or more elementary substances. Wait. Further, after forming roughened particles with copper or a copper alloy, a roughening treatment in which secondary particles or tertiary particles are provided with a simple substance or alloy of nickel, cobalt, copper, zinc, or the like may be further performed. Thereafter, a single element or alloy of nickel, cobalt, copper, zinc, or the like may be used to form a heat-resistant layer or a rust-proof layer, and the surface may be further subjected to a chromate treatment or a silane coupling treatment. Alternatively, without performing roughening treatment, a heat-resistant layer or a rust-preventive layer may be formed of a simple substance or alloy of nickel, cobalt, copper, zinc, or the like, and then the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer may be formed on the surface of the roughened layer or the alloy layer. The surface or alloy layer of the copper or copper alloy used in the exothermic material forms one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer. Further, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer may be formed in a plurality of layers (for example, two or more layers, three or more layers, etc.).

The chromate treatment layer herein means a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate, or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium (may be metals, alloys, oxides, nitrides, sulfides And so on). Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromate treated with a treatment solution containing chromic anhydride, potassium dichromate, and zinc. Processing layer, etc.

As the heat-resistant layer and rust-proof layer, a well-known heat-resistant layer and rust-proof layer can be used. For example, the heat-resistant layer and / or the rust-proof layer may also contain elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, The layer of one or more elements in the group of iron and tantalum may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, A metal layer or an alloy layer composed of one or more elements of the platinum group element, iron, and tantalum. In addition, the heat-resistant layer and / or the rust-preventive layer may contain elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, Oxides, nitrides, and silicides of one or more elements in the iron and tantalum group. The heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The above-mentioned nickel-zinc alloy layer may be one containing 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc in addition to unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer is 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , and preferably 20 to 100 mg / m ² . In addition, the ratio of the nickel adhesion amount to the zinc adhesion amount (= nickel adhesion amount / zinc adhesion amount) of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer is preferably 1.5 to 10. The nickel adhesion amount of the nickel-zinc alloy-containing layer or the nickel-zinc alloy layer is preferably 0.5 mg / m ² to 500 mg / m ² , and more preferably 1 mg / m ² to 50 mg / m ² . When the heat-resistant layer and / or rust-proof layer is a layer containing a nickel-zinc alloy, when the inner wall portion of a through hole or via hole is in contact with a desmear liquid, The interface between the copper or copper alloy or alloy layer and the resin substrate is difficult to be corroded by the deslagging solution, and the adhesion between the copper or copper alloy or alloy layer and the resin substrate will be improved.

For example, the heat-resistant layer and / or rust-proof layer may be a nickel or nickel alloy layer with an adhesion amount of 1 mg / m ² to 100 mg / m ² , preferably 5 mg / m ² to 50 mg / m ² , and an adhesion amount of 1 mg / m ² . m ² to 80 mg / m ² , preferably 5 mg / m ² to 40 mg / m ^2, the tin layers are sequentially laminated. The above nickel alloy layer may also be made of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. Any kind of composition. The total adhesion amount of nickel or nickel alloy and tin in the heat-resistant layer and / or rust-preventive layer is preferably 2 mg / m ² to 150 mg / m ² , and more preferably 10 mg / m ² to 70 mg / m ² . In addition, the heat-resistant layer and / or the rust-preventive layer is preferably [the nickel adhesion amount in nickel or a nickel alloy] / [tin adhesion amount] = 0.25 to 10, and more preferably 0.33 to 3. When this heat-resistant layer and / or rust-proof layer is used, the peeling strength of a circuit after the copper foil with a carrier is processed into a printed wiring board, and the chemical-resistance deterioration rate of this peeling strength become favorable.

Further, as the silane coupling agent used in the silane coupling treatment, a known silane coupling agent can be used, and for example, an amine-based silane coupling agent, an epoxy-based silane coupling agent, or a mercapto-based silane coupling agent can be used. Also, as the silane coupling agent, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-glycidoxy Γ-glycidoxypropyltrimethoxysilane, 4-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-amino group Propyltrimethoxysilane, N-3- (4- (3-aminopropyloxy) butoxy) propyl-3-aminopropyltrimethoxysilane, imidazolane, tris Silane, γ-mercaptopropyltrimethoxysilane and the like.

The silane coupling treatment layer may be formed using a silane coupling agent such as epoxy-based silane, amine-based silane, methacryl-based silane, or mercapto-based silane. In addition, such a silane coupling agent may be used in combination of two or more. Among them, those formed using an amine-based silane coupling agent or an epoxy-based silane coupling agent are preferred.

The so-called amine-based silane coupling agent may also be selected from the group consisting of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-benzene Vinylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethyl Oxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3-propenyloxy-2- (Hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- ( 2-aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-amine Propyl) tris (2-ethylhexyloxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropyloxy) ) -3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltri (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane , 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2-N-benzylaminoethylethylaminopropyl) trimethoxysilane, bis ( 2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N-dimethyl-3 -Aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2- Aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-Aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane.

The silane coupling treatment layer is preferably set to 0.05 mg / m ² to 200 mg / m ² in terms of silicon atom conversion, preferably 0.15 mg / m ² to 20 mg / m ² , and preferably 0.3 mg / m ² to 2.0 mg / m ² range. In the case of the above range, the adhesion between the copper or copper alloy or alloy layer and the adhesive layer used in the copper heat radiating material can be further improved.

In addition, the surfaces of copper or copper alloys, alloy layers, roughened layers, heat-resistant layers, rust-proof layers, silane coupling-treated layers, or chromate-treated layers used in copper heat-emitting materials can be described in the following documents. Surface treatment: International Publication No. WO2008 / 053878, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, International Publication No. WO2007 / 105635, Japanese Patent No. 5180815, Japanese Patent Laid-Open No. 2013-19056.

In the copper heat radiation material of the present invention, the surface of the copper base material before the alloy layer is provided can be adjusted in the following manner. This is to control the surface of the copper exothermic material to a specific state of Sz, Sa, Sku, △ E * ab, △ L, △ a, △ b, and surface area ratio.

When a rolled material is used as the copper base material, the rolled material is obtained by controlling the oil film equivalent expressed by the following formula and rolling it.

Oil film equivalent = {(rolling oil viscosity [cSt]) × (through plate speed [mpm] + roller peripheral speed [mpm])} / {(roller bite angle [rad]) × (material falling stress [kg / mm ² ])}

The rolling oil viscosity [cSt] is the dynamic viscosity at 40 ° C.

Specifically, the following rolled material was used as the copper base material of the present invention, and the rolled material was obtained by rolling with an oil film equivalent of the final cold pressing delay of 16,000 to 30,000. The reason is that in the case where it does not reach 16,000 or when it exceeds 30,000, the surface after the above-mentioned alloy layer is provided does not become a specific range. When it is less than 16000, the Sz value may become too small. When it exceeds 30,000, the Sz value may become too large.

In order to set the oil film equivalent to 16000 to 30,000, it is only necessary to use a known method such as rolling oil with a low viscosity or slowing down the plate speed.

In addition, the manufacturing conditions of the electrolytic copper foil which can be used for this invention are shown below.

<Electrolyte composition>

Copper: 90 ~ 110g / L

Sulfuric acid: 90 ~ 110g / L

Chlorine: 50 ~ 100mg / L

Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10 ~ 30ppm

Leveling agent 2 (amine compound): 10 ~ 30ppm

As the amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

<Manufacturing conditions>

Current density: 70 ~ 100A / dm ²

Electrolyte temperature: 50 ~ 60 ℃

Linear speed of electrolyte: 3 ~ 5m / sec

Electrolysis time: 0.5 ~ 10 minutes

Moreover, the surface of copper or copper alloy used in the copper heat-emitting material can be controlled by the following treatment. As the surface treatment, a surface treatment for forming unevenness on the surface of copper or a copper alloy may be applied. As a surface treatment for forming unevenness on the surface of copper or a copper alloy, a surface treatment using chemical polishing or electrolytic polishing may be performed. As a treatment liquid used in chemical polishing, an etching solution containing sulfuric acid and hydrogen peroxide, an etching solution containing ammonium fluoride, an etching solution containing sodium persulfate, and iron trichloride or copper trichloride can be used. As a liquid for general etching, such as an etchant, a well-known etchant may be used. In addition, for example, by using copper sulfate and sulfuric acid water In a solution composed of a solution, the surface of copper or a copper alloy is electrolytically polished to form irregularities on the surface. Generally speaking, electrolytic polishing is for the purpose of smoothing, but the surface treatment of the surface of copper or copper alloy used in the copper heat-generating material of the present invention uses electrolytic polishing to form irregularities, so it is contrary to the general idea idea. The method of forming unevenness by electrolytic polishing can also be performed by a well-known technique. Examples of well-known techniques for electrolytic polishing for forming the unevenness include the methods described in Japanese Patent Application Laid-Open No. 2005-240132, Japanese Patent Application No. 2010-059547, and Japanese Patent Application No. 2010-047842. Specific conditions for the process of forming unevenness by electrolytic polishing include, for example,

‧Processing solution: Cu: 10 ~ 40g / L, H ₂ SO ₄ : 50 ~ 150g / L, temperature: 30 ~ 70 ℃

‧Electrolytic grinding current: 5 ~ 40A / dm ²

‧Electrolytic grinding time: 5 ~ 50 seconds

Wait.

As a surface treatment for forming unevenness on the surface of copper or a copper alloy, for example, the unevenness may be formed by mechanically polishing the surface of copper or a copper alloy. Mechanical grinding can also be performed by well-known techniques.

Furthermore, after the surface treatment of the surface of the copper or copper alloy used in the copper heat-generating material of the present invention, a heat-resistant layer, a rust-proof layer, or a weather-resistant layer may be provided. The heat-resistant layer, the rust-proof layer, and the weather-resistant layer may be the methods described in the above-mentioned or experimental examples, or may be a well-known technical method.

The copper heat radiating material of the present invention may be further formed on the surface of the alloy layer of the copper heat radiating material with a roughening treatment layer, a heat-resistant treatment layer, a rust-proof treatment layer, and an oxide layer. Oxide layer). Further, a base layer may be provided between the copper heat-radiating material and the alloy layer so long as it does not hinder the plating constituting the alloy layer.

The copper heat-radiating material of the present invention can be bonded to a resin substrate to produce a laminated body such as a shielding material, a shielding member such as a shielding tape. In addition, if necessary, the copper heat-radiating material is further processed to form a circuit, thereby producing a printed wiring board or the like. As the resin substrate, for example, for rigid PWB, paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth / paper composite substrate epoxy resin, glass cloth / glass nonwoven fabric can be used. For composite substrate epoxy resin and glass cloth substrate epoxy resin, etc., for FPC or tape, polyester film or polyimide film, liquid crystal polymer (LCP), PET film, etc. can be used. In addition, in the present invention, the "printed wiring board" is set to include a printed wiring board, a printed circuit board, and a printed circuit board on which members are mounted. Furthermore, two or more printed wiring boards of the present invention can be connected to produce a printed wiring board connected to two or more printed wiring boards, and at least one printed wiring board of the present invention can be connected to another printed wiring board of the present invention. A board or a printed wiring board connection that does not correspond to the printed wiring board of the present invention can be used to manufacture an electronic device. In addition, in this invention, a "copper circuit" is set also including copper wiring.

In addition, the copper heat-radiating material of the present invention can be used for heat-radiating plates, structural plates, shielding materials, shielding plates, shielding members, reinforcing materials, masks, cases, cases, boxes, and the like to produce metal-processed members. The copper heat-radiating material of the present invention is excellent as a copper heat-radiating material for heat-radiation because it has good absorbability of heat emitted from the heat-generating body and the heat-releasing property of the absorbed heat. The metal-processed part is assumed to include a heat radiation plate, a structural plate, a shielding material, a shielding plate, a shielding member, a reinforcing material, a shield, a case, a case, and a box.

In addition, the copper heat-radiating material of the present invention can be used for a metal-worked member produced by using the heat-radiating plate, a structural plate, a shielding material, a shielding plate, a shielding member, a reinforcing material, a mask, a housing, a shell, a box, and the like. For electronic machines.

[Copper foil with carrier]

The copper foil with a carrier according to another embodiment of the present invention has an intermediate layer and an ultra-thin copper layer sequentially on one or both sides of the carrier. The ultra-thin copper layer is the copper heat-radiating material according to the embodiment of the present invention. The "copper foil" of the copper foil with a carrier also includes a copper alloy foil.

<Carrier>

The carrier that can be used in the present invention is typically a metal foil or a resin film, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, and insulating resin film. (For example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyimide film, a polyester film, a fluororesin film, etc.) are provided.

As a carrier usable in the present invention, copper foil is preferably used. This is because the copper foil has a high electrical conductivity, so that it is easy to form an intermediate layer and an ultra-thin copper layer later. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Generally speaking, electrolytic copper foil is produced by electrolyzing copper on a titanium or stainless steel drum using a copper sulfate plating bath, and rolled copper foil is produced by repeating plastic processing and heat treatment using a rolling roll. In addition to high-purity copper such as refined copper or oxygen-free copper, copper foil can also be made of copper alloys doped with Sn, Ag-doped copper, Cr, Zr, or Mg, and Ni and Si. Corson is a copper alloy such as a copper alloy.

The thickness of the carrier that can be used in the present invention is not particularly limited, as long as it is appropriately adjusted to a suitable thickness that can function as a carrier, for example, it can be 5 μm or more. However, if it is too thick, the production cost will increase, so it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, and more typically 18 to 35 μm.

After the surface treatment, the Sz, Sa, Sku, and surface area ratio A / B of the ultra-thin copper layer can be controlled by the same surface treatment as the copper heat-emitting material.

In addition, an electrolytic copper foil that can be produced by the following method can be used as a carrier.

<Electrolyte composition>

Copper: 90 ~ 110g / L

Sulfuric acid: 90 ~ 110g / L

Chlorine: 50 ~ 100mg / L

Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10 ~ 30ppm

Leveling agent 2 (amine compound): 10 ~ 30ppm

As the amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

<Manufacturing conditions>

Current density: 70 ~ 100A / dm ²

Electrolyte temperature: 50 ~ 60 ℃

Linear speed of electrolyte: 3 ~ 5m / sec

Electrolysis time: 0.5 ~ 10 minutes (adjusted according to the thickness of the precipitated copper and current density)

Furthermore, a roughening treatment layer may be provided on the surface of the carrier opposite to the surface on the side where the ultra-thin copper layer is provided. The roughening treatment layer can be provided using a known method, and the roughening treatment layer can also be provided by the above-mentioned roughening treatment. Providing a roughening treatment layer on the surface of the carrier opposite to the surface on which the ultra-thin copper layer is provided has the advantage that when the carrier is laminated on a support such as a resin substrate from the surface side having the roughening treatment layer, the carrier It becomes difficult to peel off from the resin substrate.

<Middle layer>

An intermediate layer is provided on the carrier. Other layers may be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it has the following structure: before the step of laminating the copper foil with a carrier to the insulating substrate, the extremely thin copper layer is not easy to peel off from the carrier; on the other hand, after the step of laminating the insulating substrate The very thin copper layer can be peeled from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may also contain a material selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, these alloys, these hydrates, One or two or more of these groups of oxides and organic substances. The intermediate layer may be a plurality of layers.

In addition, for example, the intermediate layer may be formed by forming one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn from the carrier side. A single metal layer or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A hydrate or an oxide or an organic substance of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn is formed thereon Composition of layers.

In addition, for example, the intermediate layer may be formed by forming from the carrier side an element group selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. A single metal layer composed of one element, or an alloy composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn A layer on which a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn is formed, or is selected from the group consisting of Cr , Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an alloy layer composed of one or more elements.

Moreover, as said organic substance of an intermediate | middle layer, a well-known organic substance can be used, and it is preferable to use any one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. For example, as the specific nitrogen-containing organic compound, it is preferable to use a triazole compound having a substituent, namely, 1,2,3-benzotriazole, carboxybenzotriazole, N ', N'-bis (benzo Triazolylmethyl) urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazole thiol, and the like are preferably used.

As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, hypolinolenic acid, and the like are preferably used.

In addition, for example, the intermediate layer may be formed by sequentially stacking a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer on the carrier in this order. Since the adhesion force between nickel and copper is higher than the adhesion force between chromium and copper, peeling occurs at the interface between the ultra-thin copper layer and the chromium-containing layer when the ultra-thin copper layer is peeled. In addition, nickel in the intermediate layer is expected to have a barrier effect of preventing the copper component from diffusing from the carrier to the extremely thin copper layer. The amount of deposition of nickel intermediate layer is preferably from 100μg / dm ² or more and 40000μg / ² or less dm, more preferably 100μg / dm ² or more and 4000μg / dm ² or less, more preferably 100μg / dm ² or more and 2500μg / dm ² or less, more preferably 100 μg / dm ² or more and less than 1000 μg / dm ² , and the chromium adhesion amount in the intermediate layer is preferably 5 μg / dm ² or more and 100 μg / dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a nickel plating layer on the opposite side of the carrier. The chromium layer of the intermediate layer can be provided by chromium plating or chromate treatment.

If the thickness of the intermediate layer becomes too large, the thickness of the intermediate layer will affect the Sz, Sa, Sku, surface area ratio A / B of the surface of the ultra-thin copper layer after surface treatment, so the surface of the ultra-thin copper layer The thickness of the intermediate layer on the surface of the treatment layer is preferably 1 to 1000 nm, preferably 1 to 500 nm, preferably 2 to 200 nm, preferably 2 to 100 nm, and more preferably 3 to 60 nm. Furthermore, the intermediate layer may be provided on both sides of the carrier.

<Ultra-thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer having the carrier is a copper heat-radiating material according to an embodiment of the present invention. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5 to 12 μm, and more typically 1.5 to 5 μm. In addition, before the ultra-thin copper layer is provided on the intermediate layer, a copper-phosphorus alloy or the like may be subjected to primer plating in order to reduce pinholes in the ultra-thin copper layer. Examples of the primer plating include copper pyrophosphate plating solution. Furthermore, an ultra-thin copper layer can also be provided on both sides of the carrier.

The ultra-thin copper layer of the present invention may be an ultra-thin copper layer formed under the following conditions. When the above-mentioned alloy layer is provided on the surface of the ultra-thin copper layer on the side opposite to the side in contact with the intermediate layer, in order to make the surface of the alloy layer Sz, Sa, Sku, and surface area ratio A / B within the scope of the present invention, Control Sz, Sa, Sku, surface area ratio A / B of very thin copper layer surface.

‧Electrolyte composition

Copper: 80 ~ 120g / L

Sulfuric acid: 80 ~ 120g / L

Chlorine: 30 ~ 100mg / L

Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10 ~ 30ppm

Leveling agent 2 (amine compound): 10 ~ 30ppm

As the amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

‧Manufacturing conditions

Current density: 70 ~ 100A / dm ²

Electrolyte temperature: 50 ~ 65 ℃

Linear speed of electrolyte: 1.5 ~ 5m / sec

Electrolysis time: 0.5 ~ 10 minutes (adjusted according to the thickness of the precipitated copper and current density)

[Resin layer]

The copper heat radiation material of the present invention may be provided with a resin layer on one surface or both surfaces. The surface of the copper heat-radiating material on which the resin layer is provided may also be a surface-treated surface. The resin layer may be an insulating resin layer. Furthermore, in the copper heat-generating material of the present invention, the "surface treatment surface" means: after the roughening treatment, In the case of providing a surface treatment for a heat-resistant layer, an anti-rust layer, a weather-resistant layer, etc., the surface of the copper heat-radiating material after the surface treatment was performed. When the copper heat-radiating material is an ultra-thin copper layer with a copper foil with a carrier, the "surface-treated surface" refers to a surface provided with a heat-resistant layer, a rust-proof layer, and a weather-resistant layer after the roughening treatment. In the case of treatment, the surface of the ultra-thin copper layer after the surface treatment was performed.

The resin layer may be an adhesive or an insulating resin layer in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which there is no stickiness even when the surface is touched with a finger, and the insulating resin layer can be stacked and stored, and further heat treatment will cause a hardening reaction.

The resin layer may be a resin, that is, an adhesive, or an insulating resin layer in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which there is no stickiness even when the surface is touched with a finger, and the insulating resin layer can be stacked and stored, and further heat treatment will cause a hardening reaction.

The resin layer may contain a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The resin layer may contain a well-known resin, a resin hardener, a compound, a hardening accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, those described in the following documents (resin, resin hardener, compound, hardening accelerator, dielectric, reaction catalyst, crosslinker, polymer, prepreg, skeleton material, etc.) ) And / or a method for forming a resin layer and a forming apparatus, the document is International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Kaiping No. 11-140281, Japanese Patent No. 3184485, International Publication No. WO97 / 02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225 No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506 No., Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923 , Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japan Japanese Patent Application Laid-Open No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Patent Laid-Open No. 2011-14727 No., International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, Japanese Patent Laid-Open No. 2013-19056.

In addition, the kind of the resin layer is not particularly limited, and preferably includes, for example, a resin containing one or more members selected from the group consisting of epoxy resin, polyimide resin, and polyfunctional cyanate. Compounds, maleimide compounds, polymaleimide compounds, maleimide resins, aromatic maleimide resins, polyvinyl acetal resins, Urethane resin, polyether fluorene (also known as polyethersulphone, polyethersulfone), polyether fluorene (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamine resin, aromatic polyamine resin polymer, rubbery Resin, Polyamine, Aromatic Polyamine, Polyamidamine / Imine Resin, Rubber Modified Epoxy Resin, Phenoxy Resin, Carboxy Modified Acrylonitrile-Butadiene Resin, Polyphenylene Ether, Dicis butadiene Difluorene Imine three Resin, thermosetting polyphenylene ether resin, cyanate ester resin, anhydride of carboxylic acid, anhydride of polycarboxylic acid, linear polymer with crosslinkable functional group, polyphenylene ether resin, 2,2- Bis (4-cyanatephenyl) propane, phosphorus-containing phenolic compounds, manganese naphthenate, 2,2-bis (4-epoxypropylphenyl) propane, polyphenylene ether-cyanate resin , Siloxane modified polyamidoimide resin, cyanate resin, phosphazene resin, rubber modified polyamidoimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyraldehyde, Phenoxy, polymer epoxy resin, aromatic polyamidoamine, fluororesin, bisphenol, block copolymer polyamidoimide resin and cyanate resin.

Moreover, the said epoxy resin type has a 2 or more epoxy group in a molecule | numerator, and can be used especially without a problem as long as it can be used for an electrical and electronic material use. The epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more epoxypropyl groups in the molecule. In addition, one or two or more kinds selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol can be used in combination. AD epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolac epoxy resin, naphthalene ring Oxygen resin, brominated bisphenol A epoxy resin, o-cresol novolac epoxy resin, rubber modified bisphenol A epoxy resin, epoxy amine epoxy resin, triglycidyl isocyanurate , N, N-glycidylamine compounds such as diglycidyl aniline, propylene oxide compounds such as diglycidyl tetrahydrophthalate, epoxy resin containing phosphorus, biphenyl epoxy resin, Novolac-type epoxy resin, trihydroxyphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin, or a hydrogenated or halogenated body of the above-mentioned epoxy resin can be used.

As the phosphorus-containing epoxy resin, a well-known phosphorus-containing epoxy resin can be used. The above-mentioned phosphorus-containing epoxy resin is preferably, for example, a derivative derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Obtained in the form of epoxy resin.

(When the resin layer contains a dielectric (dielectric filler))

The resin layer may contain a dielectric body (dielectric body filler).

When a dielectric body (dielectric body filler) is contained in any of the above-mentioned resin layers or resin compositions, it can be used to form a capacitor layer and increase the capacitance of a capacitor circuit. The dielectric body (dielectric body filler) uses BaTiO ₃ , SrTiO ₃ , Pb (Zr-Ti) O ₃ (commonly referred to as PZT), and PbLaTiO ₃ . PbLaZrO (commonly referred to as PLZT), SrBi ₂ Ta ₂ O ₉ (commonly referred to as SBT), and dielectric powders of composite oxides having a perovskite structure.

The dielectric body (dielectric body filler) may be powdered. In the case where the dielectric body (dielectric filler) is powdery, the powder characteristics of the dielectric body (dielectric filler) are preferably 0.01 μm to 3.0 μm, and more preferably 0.02 μm to 2.0. μm range. Furthermore, a scanning electron microscope (SEM) is used to take a picture of the dielectric body. When a straight line is drawn on the particles of the dielectric body in the picture, the straight line length of the particles that cross the dielectric body is the longest. The particle length of a part of the dielectric is set to the particle diameter of the dielectric. In addition, the average value of the particle diameter of the dielectric body in the measurement field is defined as the particle diameter of the dielectric body.

The resin and / or resin composition and / or compound contained in the resin layer is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N -Methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl fibrinolysin, N-methyl-2-pyrrole A resin solution (resin varnish) is prepared in a solvent such as pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, and the like. It is coated on the roughened surface of the above-mentioned copper heat radiating material, such as a roll coating method, and then is heated and dried as necessary to remove the solvent and become a B-stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. A solvent can be used to dissolve the composition of the resin layer, and the resin solid content is 3wt% to 70wt%, preferably 3wt% to 60wt%, preferably 10wt% to 40wt%, and more preferably 25wt% to 40wt%. Of resin liquid. Furthermore, from the viewpoint of the environment, it is best to dissolve it using a mixed solvent of methyl ethyl ketone and cyclopentanone at this stage. The solvent is preferably a solvent having a boiling point in the range of 50 ° C to 200 ° C.

The resin layer is preferably a semi-hardened resin film having a resin flow rate in the range of 5% to 35% when measured in accordance with MIL-P-13949G in the MIL standard.

In the description of this case, the so-called resin flow rate refers to MIL-P-13949G in the MIL standard. Four copper 10 cm square samples were taken from a copper heat-emitting material with a resin thickness of 55 μm. In the state where the samples are stacked (laminated body), the bonding is performed under the conditions of a pressing temperature of 171 ° C, a pressing pressure of 14 kgf / cm ² and a pressing time of 10 minutes. Based on the result obtained by measuring the resin outflow weight at this time, based on the number 2 Calculated value.

The copper heat radiating material (copper heat radiating material with resin) provided with the resin layer is used in a state in which the resin layer is overlapped with the base material, and then the whole is thermally pressure-bonded to thermally harden the resin layer, followed by copper heat radiation When the material is an ultra-thin copper layer with a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface of the middle layer side of the ultra-thin copper layer is exposed). A specific wiring pattern is formed on the surface on the opposite side of the roughening treatment side.

If the copper heat-emitting material with resin is used, the number of prepreg materials used in manufacturing a multilayer printed wiring board can be reduced. In addition, even if the thickness of the resin layer is set to a thickness capable of ensuring interlayer insulation, or a prepreg material is not used at all, a metal-clad laminated board can be manufactured. At this time, an insulating resin primer may be applied to the surface of the substrate to further improve the surface smoothness.

Furthermore, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination step becomes simple, so it is economically advantageous, and has the following advantages: only the prepreg body is manufactured The thickness of the multilayer printed wiring board having a thickness of material is reduced, and an extremely thin multilayer printed wiring board having a thickness of 100 μm or less can be manufactured.

The thickness of the resin layer is preferably 0.1 to 120 μm.

If the thickness of the resin layer is less than 0.1 μm, there is a case where the adhesive force is reduced, and when the copper heat-radiating material with resin is laminated on a substrate provided with an inner layer material without interposing a prepreg, it is difficult to secure the inner layer. Interlayer insulation between the layer material and the circuit. On the other hand, if the thickness of the resin layer is greater than 120 μm, it may be difficult to form a resin layer having a target thickness in one coating step, and an excessive material cost and number of steps are required, which is economically disadvantageous. .

When a copper heat-emitting material having a resin layer is used to manufacture an extremely thin multilayer printed wiring board, the thickness of the resin layer is set to 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, and more preferably When the thickness is 1 μm to 5 μm, the thickness of the multilayer printed wiring board can be reduced, so it is preferable.

Hereinafter, some examples of the manufacturing steps of the printed wiring board using the copper foil with a carrier of this invention are shown.

An embodiment of a method for manufacturing a printed wiring board of the present invention includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; and After laminating the copper foil with a carrier and the insulating substrate such that the side of the ultra-thin copper layer and the insulating substrate face each other, a step of peeling the carrier of the copper foil with a carrier is formed to form a metal-clad laminated board. Any of the addition method, the modified semi-addition method, the partial addition method, and the subtraction method forms a circuit. The insulating substrate can also be used as an inner circuit entrance.

In the present invention, the so-called semi-additive method refers to a method of performing a thin electroless plating on an insulating substrate or a metal foil seed layer to form a pattern, and then forming a conductor pattern by electroplating and etching.

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After the above-mentioned copper foil with a carrier and an insulating substrate are laminated, the carrier of the above-mentioned copper foil with a carrier is peeled off; the ultra-thin copper layer exposed by peeling off the carrier is completely removed by etching or etching using an etching solution such as an acid; or A through hole or / and a blind hole is provided on the resin exposed by removing the ultra-thin copper layer by etching; a slag removal treatment is performed on the area containing the through hole or / and the blind hole; An electroless plating layer is provided in the area of the hole or / and the blind hole; a plating resist is provided on the electroless plating layer; the plating resist is exposed, and thereafter, the plating in the area where the circuit is formed is removed A resist; providing an electrolytic plating layer in an area where the above-mentioned circuit is formed from which the above-mentioned plating resist has been removed; removing the above-mentioned plating resist; and removing the presence of the circuit except for the above-mentioned circuit by rapid etching or the like Electroless plating cladding layer region outside the domain.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After laminating the copper foil with a carrier and an insulating substrate, Carrier copper foil with carrier is peeled off; the ultra-thin copper layer exposed by peeling the carrier is completely removed by etching using an etching solution such as an acid or a plasma; and the ultra-thin copper layer exposed by removing the above-mentioned carrier by etching An electroless plating layer is provided on the surface of the resin; a plating resist is provided on the electroless plating layer; the plating resist is exposed, and thereafter, the plating resist in the area where the circuit is formed is removed; An electrolytic plating layer is provided in the above-mentioned circuit-formed area where the above-mentioned plating resist is removed; the above-mentioned plating resist is removed; and electroless plating located in a region other than the above-mentioned area where the circuit is formed is removed by rapid etching or the like Layer and very thin copper layer.

In the present invention, the so-called modified semi-additive method refers to laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and thickening a copper of the circuit forming portion by electrolytic plating, and then removing A method for forming a circuit on an insulating layer by removing a metal foil other than the above-mentioned circuit forming portion by (fast) etching using a resist.

Therefore, one embodiment of a method for manufacturing a printed wiring board of the present invention using an improved semi-additive method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After laminating the copper foil with a carrier and an insulating substrate, the carrier of the copper foil with a carrier is peeled off; through holes or / and blind holes are provided on the ultra-thin copper layer and the insulating substrate that are exposed by peeling the carrier; Holes and / or blind holes are subjected to slag removal treatment; an electroless plating layer is provided in the above-mentioned areas containing through holes or / and blind holes; a plating resist is provided on the surface of the ultra-thin copper layer exposed by peeling the carrier After the plating resist is provided, a circuit is formed by electrolytic plating; the plating resist is removed; and the ultra-thin copper layer exposed by removing the plating resist is removed by rapid etching.

In addition, the step of forming a circuit on the resin layer may be the following step: bonding another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer, and bonding to the resin The layer of copper foil with a carrier forms the above circuit. In addition, another copper foil with a carrier bonded to the resin layer may be the copper foil with a carrier of the present invention. The step of forming a circuit on the resin layer may be performed by any one of a semi-additive method, a modified semi-additive method, a partial addition method, or a subtractive method. Moreover, the copper foil with a carrier which forms a circuit on the said surface may have a board | substrate or a resin layer on the surface of the copper foil with a carrier.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using an improved semi-additive method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After the copper foil with a carrier and the insulating substrate are laminated, the carrier with the copper foil with a carrier is peeled off; a plating resist is provided on the very thin copper layer exposed by peeling the carrier; the plating resist is exposed, and thereafter Remove the plating resist in the area where the circuit is formed; set an electrolytic plating layer in the above-mentioned area where the circuit is formed with the plating resist removed; remove the plating resist; and remove The electroless plating layer and the ultra-thin copper layer in a region other than the region where the circuit is formed.

In the present invention, the so-called partial addition method refers to adding a catalyst core to a substrate formed by providing a conductive layer and, if necessary, passing through a through hole or an auxiliary hole, and forming a conductive circuit by etching, A method of manufacturing a printed wiring board by providing a solder resist or a plating resist as required, and then thickening a through hole or an auxiliary hole by an electroless plating process on the conductor circuit.

Therefore, one embodiment of a method for manufacturing a printed wiring board of the present invention using a partial addition method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After the copper foil with a carrier and the insulating substrate are laminated, the carrier with the copper foil with a carrier is peeled off; through holes or / and blind holes are provided on the ultra-thin copper layer and the insulating substrate that are exposed by peeling the carrier; And / or blind hole removal Treatment; providing a catalyst core in the above-mentioned area containing through holes and / or blind holes; setting an etching resist on the surface of the ultra-thin copper layer exposed by peeling the carrier; exposing the etching resist to form a circuit pattern; using The etching of the etching solution such as acid or the plasma etc. method removes the ultra-thin copper layer and the catalyst core to form a circuit; the removal of the above-mentioned etching resist; A thin copper layer and the surface of the insulating substrate exposed by the catalyst core are provided with a solder resist or a plating resist; and an electroless plating layer is provided in an area where the solder resist or the plating resist is not provided.

In the present invention, the subtractive method refers to a method of selectively removing unnecessary portions of a copper foil on a metal-clad laminate by etching or the like to form a conductor pattern.

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After laminating the copper foil with a carrier and an insulating substrate, peel off the carrier of the copper foil with a carrier; set a through hole or / and a blind hole on the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier; / And the blind hole area to remove the slag treatment; the above area containing the through hole or / and blind hole is provided with an electroless plating layer; the above electroless plating layer is provided with an electrolytic plating layer on the above surface; An etching resist is provided on the surface of the cladding layer or / and the above-mentioned ultra-thin copper layer; the above-mentioned etching resist is exposed to form a circuit pattern; the above-mentioned ultra-thin copper layer and the above-mentioned are removed by etching or plasma using an etching solution such as an acid or the like Forming an electric circuit by using an electroless plating layer and the electrolytic plating layer; and removing the etching resist.

Another embodiment of the manufacturing method of the printed wiring board of the present invention using the subtractive method includes the following steps: preparing the copper foil with a carrier and an insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After the carrier copper foil and the insulating substrate are laminated, Carrier copper foil carrier peeling; through holes or / and blind holes are provided on the ultra-thin copper layer and the insulating substrate exposed by peeling the above carrier; the area containing the above through holes or / and blind holes is subjected to degreasing treatment; An electroless plating layer is provided in the above-mentioned area containing a through hole or / and a blind hole; a mask is formed on the surface of the aforementioned electroless plating layer; an electrolytic plating layer is provided on the surface of the aforementioned electroless plating layer where no mask is formed ; Setting an etching resist on the surface of the electrolytic plating layer or / and the ultra-thin copper layer; exposing the etching resist to form a circuit pattern; using etching or plasma using an etching solution such as acid to remove the electrode Forming a circuit with the thin copper layer and the electroless plating layer; and removing the etching resist.

The step of setting through holes and / or blind holes, and the subsequent step of removing glue residue may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier which concerns on this invention is demonstrated in detail. Here, a copper foil with a carrier having an ultra-thin copper layer formed with a roughened layer will be described as an example, but it is not limited to this. The carrier copper foil can be similarly subjected to the following method for producing a printed wiring board.

First, a copper foil with a carrier (first layer) having an ultra-thin copper layer having a roughened layer formed on the surface is prepared.

Next, a resist is applied to the roughened layer of the ultra-thin copper layer, and the resist is exposed to a specific shape by exposure and development.

Secondly, a circuit plating layer having a specific shape is formed by removing the resist after the circuit plating layer is formed.

Secondly, the resin layer is laminated on the ultra-thin copper layer by covering the circuit plating layer (by burying the circuit plating layer), and then another copper foil with a carrier (the 2 layer).

Next, the carrier was peeled from the copper foil with a carrier of the second layer.

Secondly, laser drilling is performed at a specific position of the resin layer to expose the circuit plating layer and form blind holes.

Secondly, copper is buried in the blind holes to form a via filling.

Next, a circuit plating layer is formed on the via hole filling material in the manner described above.

Next, the carrier was peeled from the copper foil with a carrier in the first layer.

Secondly, the ultra-thin copper layers on both surfaces are removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Second, a bump is formed on the circuit plating layer in the resin layer, and a copper pillar is formed on the solder. In this way, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The other copper foil with a carrier (the second layer) described above may use the copper foil with a carrier of the present invention, or may use the previous copper foil with a carrier, and may further use a common copper foil. Furthermore, one layer or a plurality of layers of circuits can be further formed on the above-mentioned second layer circuit, and these can be formed by any one of a semi-additive method, a subtractive method, a partial additive method, or an improved semi-additive method. Circuit.

Further, as the resin, a known resin or prepreg can be used. It is possible to use, for example, BT (biscis ) Resin or glass cloth impregnated with BT resin is prepreg, ABF film or ABF manufactured by Ajinomoto Fine-Techno Co., Ltd. In addition, as the embedded resin (resin), a resin layer and / or a resin and / or a prepreg described in this specification may be used.

The copper foil with a carrier used in the first layer may have a substrate or a resin layer on a surface of the copper foil with a carrier. By having the substrate or the resin layer, the carrier used in the first layer The bulk copper foil is supported, and wrinkles are less likely to occur. Therefore, there is an advantage that productivity is improved. In addition, as long as the said substrate or resin layer has the effect which supports the copper foil with a carrier used for the said 1st layer, all the substrate or resin layers can be used. For example, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a plate of an inorganic compound, a plate of an organic compound, or a well-known carrier described in the specification of the present case can be used. An organic compound foil is used as the substrate or resin layer.

The copper heat radiation material of the present invention can be laminated to a resin substrate from the surface treatment layer side or the side opposite to the surface treatment layer side to produce a laminated body. The resin substrate is not particularly limited as long as it has characteristics applicable to printed wiring boards. For example, for rigid PWB, paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, Fluorine resin impregnated knitted fabric, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven fabric composite substrate epoxy resin, glass cloth substrate epoxy resin, etc. can be used for flexible printed circuit boards (FPC) Polyester film or polyimide film, liquid crystal polymer (LCP) film, fluororesin and fluororesin-polyimide composite material, etc. Furthermore, since the liquid crystal polymer (LCP) has a small dielectric loss, the liquid crystal polymer (LCP) film can be preferably used for a printed wiring board for high-frequency circuit applications.

Regarding the bonding method, in the case of a rigid PWB, a prepreg in which a resin is impregnated into a substrate such as glass cloth and the resin is cured to a semi-hardened state is prepared. It can be performed by superimposing a copper foil and a prepreg, and heating and pressing. In the case of FPC, a substrate such as a liquid crystal polymer or a polyimide film can be laminated to a copper foil at a high temperature and pressure by using an adhesive, or without using an adhesive, or a polyimide precursor The laminated body is produced by coating, drying, curing, and the like.

The laminated body of the present invention can be used for various printed wiring boards (PWB), and there is no special For example, from the viewpoint of the number of layers of the conductor pattern, it can be applied to single-sided PWB, double-sided PWB, and multilayer PWB (3 or more layers). From the viewpoint of the type of insulating substrate material, it can be applied to rigid PWB. , Flexible PWB (FPC), soft and hard composite PWB.

In addition, the copper heat-generating material of the present invention or the copper foil with a carrier of the present invention may be laminated with a resin substrate or a substrate from a surface-treated layer side or a side opposite to the surface-treated layer side (also metal materials, inorganic materials, organic materials) , Ceramics) or housings or metal-machined components or electronic parts or electronic machines or liquid crystal panels or displays to produce a laminated body.

The laminated body may have an adhesive layer or an adhesive layer between the copper heat-generating material of the present invention or the copper foil with a carrier of the present invention and the resin substrate or the substrate. The adhesive layer may be a layer using a conductive adhesive or a layer using a conductive acrylic adhesive. The resin substrate or the substrate may be a separator. The separator refers to a resin substrate or a substrate capable of peeling an adhesive layer or an adhesive layer from the copper heat-generating material of the present invention or the copper foil with a carrier of the present invention from the laminated body. The copper heat radiating material of the present invention or the copper foil with a carrier of the present invention may be peelable from the resin substrate or the substrate.

When the laminated system has a laminated body having an adhesive layer or an adhesive layer between the copper heat-generating material of the present invention or the copper foil with a carrier of the present invention and the resin substrate or the substrate, the copper heat-generating material of the present invention or The copper foil with a carrier of the present invention may be peelable from the resin substrate or the substrate.

In the above case, if the copper heat-generating material of the present invention or the copper foil with a carrier of the present invention is peeled from the resin substrate or the substrate, an adhesive layer or an adhesive layer is applied to the copper heat-emitting material of the present invention or the carrier with the present invention. The surface of the copper foil is exposed. Therefore, the copper heat-generating material of the present invention or the copper foil with a carrier of the present invention can also be layered with other materials after the resin substrate or the substrate is peeled off. The laminated body may also have the copper heat-generating material of the present invention or the accessory of the present invention on both sides of the resin substrate or the substrate. Carrier copper foil.

In addition, as the adhesive layer and the adhesive layer, a known adhesive, an adhesive, a resin layer described in this specification, and a resin usable in the resin layer described in this specification can be used.

Furthermore, a printed wiring board and a copper-clad laminated board can be manufactured using the copper heat radiation material of this invention. Moreover, the printed wiring board manufactured using the copper material of this invention can be used for an electronic device. In addition, the copper material of the present invention can also be used for the production of a negative electrode current collector for a secondary battery, a secondary battery, a support substrate used in a coreless multilayer printed wiring board, and the like.

‧Examples 1 to 11, 13 to 18, and Comparative Examples 1 to 8.

As Examples 1 to 11, 13 to 18, and Comparative Examples 1 to 8, various copper substrates having thicknesses described in Tables 1 to 4 were prepared. Next, an alloy layer is formed on the copper substrate. At this time, as shown in Tables 1 to 4, the layers were formed in the order of (1) to (3).

‧Example 12

As the base material of Example 12, a copper foil with a carrier as described below was prepared. First, an electrolytic copper foil of JTC foil manufactured by JX Nippon Nissei Metal Co., Ltd. with a thickness of 18 μm was prepared as a carrier. Next, an intermediate layer is formed on the surface on the glossy surface side of the carrier, and an extremely thin copper layer is formed on the surface of the intermediate layer under the following conditions.

<Middle layer>

(1) Ni layer (Ni plating)

The carrier was electroplated by a roll-to-roll continuous plating line under the following conditions to form a Ni layer with an adhesion amount of 1000 μg / dm ² . The specific plating conditions are as follows: Nickel sulfate: 270 ~ 280g / L

Nickel chloride: 35 ~ 45g / L

Nickel acetate: 10 ~ 20g / L

Boric acid: 30 ~ 40g / L

Gloss agent: saccharin, butynediol

Sodium Lauryl Sulfate: 55 ~ 75ppm

pH: 4 ~ 6

Bath temperature: 55 ~ 65 ℃

Current density: 10A / dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, the surface of the Ni layer formed in (1) was washed with water and pickled, and then subjected to electrolytic chromate treatment on a roll-to-roll continuous plating line under the following conditions, so that the adhesion amount was 11 μg / dm. The Cr layer of ² is attached to the Ni layer.

Potassium dichromate: 1 ~ 10g / L

pH value: 7 ~ 10

Liquid temperature: 40 ~ 60 ℃

Current density: 2A / dm ²

<Ultra-thin copper layer>

Next, the surface of the Cr layer formed in (2) was washed with water and pickled, and then plated on a roll-to-roll continuous plating line under the following conditions to form a 5 μm-thick electrode on the Cr layer. A thin copper layer was used to produce a very thin copper foil with a carrier.

Copper concentration: 90 ~ 110g / L

Sulfuric acid concentration: 90 ~ 110g / L

Chloride ion concentration: 50 ~ 90ppm

Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10 ~ 30ppm

Leveling agent 2 (amine compound): 10 ~ 30ppm

The following amine compound was used as the leveling agent 2.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

Electrolyte temperature: 50 ~ 80 ℃

Current density: 100A / dm ²

Linear speed of electrolyte: 1.5 ~ 5m / sec

‧Sz, Sa, Sku on the surface; Using a laser microscope OLS4000 (LEXT OLS 4000) made by Olympus, the Sz, Sa, and Sku on the surface of the copper heat sink was measured according to ISO25178. Using a 50x objective lens of a laser microscope, an area of about 200 μm × 200 μm (specifically, 40 106 μm ² ) was measured to calculate Sz, Sa, and Sku. In addition, in the case of laser microscope measurement, when the measurement surface of the measurement result is not a flat surface but a curved surface, Sz, Sa, and Sku are calculated after plane correction. Furthermore, the measurement ambient temperature of Sz, Sa, and Sku measured with a laser microscope was 23 to 25 ° C.

‧Surface area ratio A / B; Using a laser microscope OLS4000 (LEXT OLS 4000) made by Olympus, the surface area of the copper heat-radiating material surface was measured according to ISO25178, and the surface area ratio A / B was calculated using it. The measurement was performed using a 50-fold objective lens of a laser microscope with an area of about 200 μm × 200 μm (specifically, 40 106 μm ² ). In addition, the measured ambient temperature of the three-dimensional surface area A measured by a laser microscope was 23 to 25 ° C.

‧Color aberration: The color aberration measured by HunterLab Co., Ltd. MiniScan XE Plus according to JISZ8730 is as follows: the white plate on the surface of the copper exothermic material (the light source is set to D65, and when the field of view is set to 10 degrees, the white plate The three stimulus values of the X ₁₀ Y ₁₀ Z ₁₀ color system (JIS Z8701 1999) are X ₁₀ = 80.7, Y ₁₀ = 85.6, Z ₁₀ = 91.5, and the white color in the L ^* a ^* b ^* color system The case where the object color of the board is L ^* = 94.14, a ^* =-0.90, b ^* = 0.24) is set as the reference color. Furthermore, in the above-mentioned color difference meter, the measurement value of the color difference of the white plate is set to ΔE ^* ab = 0, and the measurement value of the color difference when the measurement hole is covered with a black trap (light trap) for measurement is set to ΔE. ^* ab = 94.14 to correct chromatic aberration. Here, the color difference ΔE ^* ab is defined as zero for the white plate and 94.14 for black. In addition, the color difference ΔE ^* ab measured in accordance with JIS Z8730 for minute areas such as copper circuit surfaces can be a micro-surface spectrophotometer (model: VSS400, etc.) manufactured by Nippon Denshoku Industries Co., Ltd. or Suga Test Instruments Co., Ltd., a micro-surface spectrophotometer (model: SC-50μ, etc.) and other known measuring devices.

‧Falling powder: As for the falling powder, a transparent mending tape is affixed to the surface. When the tape is peeled off, the tape changes color due to the falling particles attached to the adhesive surface of the tape. powder.

A case where the tape did not change color was ◎, a case where the tape changed to gray was ○, and a case where the tape changed to black was ×.

‧ Emissivity; FT-IR: Fourier Transform Infrared Spectroscopy (FT-IR) was used to measure the reflectance spectrum on the surface of the copper exothermic material under the following conditions to calculate the emissivity.

(1) Evaluation of heat release

As shown in Figure 1, a heating element with a length of d1 × w1 × thickness h1 = 5mm × 5mm × 1mm is set in the center of the surface of the substrate (Mg alloy die casting) with a length of d2 × width w2 × thickness h2 = 50mm × 100mm × 0.2mm (The heating element with the heating wire fixed by resin is equivalent to an IC chip). Then, an adhesive layer (length d3 × width w3 × thickness h3 = 50mm × 100mm × 0.03mm) is provided on the surface opposite to the heating element of the substrate, and from the surface on the opposite side to the surface on which the alloy layer is formed, The copper heat-radiating material of this example and comparative example (length d4 × width w4 × thickness h4 = 50mm × 100mm × thickness of the copper base material described in the table) was laminated. Then, a thermocouple was installed on the "central portion of the heating element" and "the position corresponding to the central portion of the heating element on the surface of the copper heat-radiating material opposite to the surface of the adhesive layer". A schematic diagram of the upper surface of the sample is shown in FIG. 1. A schematic cross-sectional view of the sample is shown in FIG. 2.

Then, an electric current was caused to flow into the heating element so that the heat generation amount became 0.5 W. Then, an electric current flows so that the temperature of the center part of the upper surface of the heating element becomes a constant value. Here, when the temperature of the central portion of the upper surface of the heating element does not change within 10 minutes, it is determined that the temperature of the central portion of the upper surface is a constant value. The external ambient temperature was set to 20 ° C. Then, after the temperature at the central portion of the upper surface of the heating element became constant and maintained for 30 minutes, the display temperature of the thermocouple provided on the copper heat-emitting material was measured. Next, the lower display temperature of the thermocouple was judged to be good. Furthermore, the surface of the copper heat-radiating material opposite to the surface of the adhesive layer is corresponding to the central portion of the heating element. The position is the highest temperature position in the copper heat sink.

(2) Measurement of reflectance

The wavelength of light of each of the above samples was measured under the following conditions. The measurement was performed twice by rotating the measurement direction in the measurement plane of the sample by 90 degrees.

Measuring device: IFS-66v (FT-IR manufactured by Bruker, vacuum optical system)

Light source: Incandescent rod (SiC)

Detector: MCT (HgCdTe)

Beamsplitter: Ge / KBr

Measurement conditions: resolution = 4cm ^-1

Cumulative times: 512 times

Zero filling = 2 times

Apodization method = triangle

Measurement area = 5000 ~ 715cm ^-1 (wavelength of light: 2 ~ 14μm)

Measurement temperature = 25 ℃

Additional device: Integrating sphere for measuring transmittance and reflectance

Port diameter = 10mm

Repeat accuracy = about ± 1%

Reflectance measurement

Angle of incidence: 10 degrees

Reference sample: diffuse gold (Infragold-LF Assembly)

No specular cup (removal of specular reflection device)

(3) About emissivity

The light incident on the sample surface is absorbed internally, in addition to the reflected and transmitted light. Regarding the absorptivity (α) (= emissivity (ε)), reflectance (r), and transmittance (t), the following formulas are established.

ε + r + t = 1 (A)

The emissivity (ε) can be calculated from the reflectance and transmittance by the following general formula.

ε = 1-r-t (B)

When the sample is opaque and thick enough to ignore penetration, etc., t = 0 and the emissivity can only be determined from the reflectance.

ε = 1-r (C)

Since infrared rays are not transmitted in this sample, the formula (C) is applied to calculate the emissivity of each light wavelength.

(4) FT-IR spectrum

The average of the results of the two measurements was taken as the reflectance spectrum. The reflectance spectrum is corrected by the reflectance of diffuse gold. (Display wavelength range: 2 ~ 14μm)

Here, if the radiation energy distribution of a black object at a temperature obtained by using the formula of Blank is set, the energy intensity at each wavelength λ is set to E _{b λ} , and the emissivity of the sample at each wavelength λ is set to ε λ, Then the sample radiation energy intensity E _{s λ is} expressed as E _{s λ} = ε λ‧E _{b λ} . In this embodiment, the formula: E _{s λ} = ε _{λ ·} E _{b λ} is used to obtain the radiation energy intensity E _{s λ} of each sample at 25 ° C.

In addition, the total energy of black objects and samples in certain wavelength regions is obtained by using the integral value of E _{s λ} and E _{b λ} in the wavelength range, and the total emissivity ε is expressed by the ratio (below Said formula A). In this embodiment, this formula is used to calculate the total emissivity ε of each sample in a wavelength region of 2 to 14 μm at 25 ° C. The total emissivity ε obtained is then set as the emissivity of each sample.

The conditions and test results of the above tests are shown in Tables 1 to 4.

(Evaluation results)

Examples 1 to 18 had good exothermic properties.

In Comparative Examples 1 to 3 and 5 to 8, none of the alloy layers were formed, and the surface roughness Sz of the surface was outside the range of 5 μm or more, and the exothermic properties were poor compared with the examples.

Comparative Example 4 uses a stainless steel substrate, and has a lower exothermic property than the examples.

In addition, in the above-mentioned embodiment, the same characteristics can be obtained by performing the same alloy layer forming treatment on both surfaces of the copper substrate.

Claims (40)

A copper exothermic material, an alloy layer containing one or more metals selected from the group consisting of Cu, Co, Ni, W, P, Zn, Cr, Fe, Sn, and Mo is formed on one or both sides, and a laser light wavelength is used. The surface roughness Sz of one or both of the surfaces measured by a laser microscope of 405 nm is 5 μm or more. For example, the copper heat-generating material according to the first patent application scope, wherein the surface roughness Sz of one or both of the surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 7 μm or more. For example, the copper heat-generating material in the second item of the patent application scope, wherein the surface roughness Sz of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 10 μm or more. For example, the copper heat-generating material in the third item of the patent application scope, wherein the surface roughness Sz of the one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 14 μm or more. For example, the copper heat-generating material according to any one of claims 1 to 4, wherein the surface roughness Sz of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 90 μm or less. For example, the copper heat-generating material according to the first patent application scope, wherein the surface roughness Sa of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 0.13 μm or more. For example, the copper exothermic material in the first item of the patent application scope, wherein the surface roughness Sku of one or both of the surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 6 or more. For example, the copper heat-generating material according to item 6 of the application, wherein the surface roughness Sku of one or both of the surfaces measured by a laser microscope with a laser light wavelength of 405 nm is 6 or more. For example, the copper heat-generating material in the first scope of the patent application, wherein the surface area of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is set to A, and the area in plan view is set to B. The surface area ratio A / B is 1.35 or more. For example, the copper heat-generating material in the sixth scope of the patent application, wherein the surface area of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is set to A, and the area in plan view is set to B. The surface area ratio A / B is 1.35 or more. For example, the copper heat-generating material in the seventh scope of the patent application, wherein the surface area of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is set to A, and the area in plan view is set to B. The surface area ratio A / B is 1.35 or more. For example, the copper heat-generating material under the scope of patent application No. 8 in which the surface area of one or both surfaces measured by a laser microscope with a laser light wavelength of 405 nm is set to A, and the area in plan view is set to B The surface area ratio A / B is 1.35 or more. For example, the copper heat-radiating material according to any one of the claims 1, 6 to 12, in which the color difference ΔL based on JISZ8730 of the one or both surfaces satisfies ΔL ≦ -35. For example, the copper heat-radiating material according to any one of the claims 1, 6 to 12, in which the color difference Δa based on JISZ8730 on one or both surfaces satisfies Δa ≦ 15. For example, the copper heat-radiating material according to item 13 of the patent application scope, in which the color difference Δa based on JISZ8730 on one or both surfaces satisfies Δa ≦ 15. For example, the copper heat-radiating material according to any one of claims 1, 6 to 12, in which the color difference Δb based on JISZ8730 on one or both surfaces satisfies Δb ≦ 17. For example, the copper heat-radiating material according to item 13 of the patent application scope, in which the color difference Δb based on JISZ8730 on one or both surfaces satisfies Δb ≦ 17. For example, the copper heat-radiating material according to item 14 of the patent application scope, wherein the color difference Δb based on JISZ8730 on one or both surfaces satisfies Δb ≦ 17. For example, the copper heat-radiating material according to item 15 of the patent application scope, wherein the color difference Δb based on JISZ8730 of the above one or two surfaces satisfies Δb ≦ 17. For example, the copper heat-radiating material according to any one of claims 1, 6 to 12, wherein the emissivity of one or both of the above surfaces is 0.092 or more. For example, the copper exothermic material in the scope of application for item 13, wherein the emissivity of the above one or both surfaces is above 0.092. For example, the copper exothermic material in the scope of application for patent No. 14, wherein the emissivity of the above one or both surfaces is above 0.092. For example, the copper heat-radiating material under the scope of application for patent No. 15, wherein the emissivity of the above one or both surfaces is above 0.092. For example, for the copper heat-radiating material under the scope of application for patent No. 16, wherein the emissivity of the above one or both surfaces is above 0.092. For example, for the copper heat-radiating material under the scope of application for patent No. 17, the emissivity of the above one or both surfaces is above 0.092. For example, the copper exothermic material in the scope of application for patent No. 18, wherein the emissivity of the above one or both surfaces is above 0.092. For example, the copper exothermic material in the scope of patent application No. 19, wherein the emissivity of the above one or both surfaces is above 0.092. For example, the copper heat-radiating material according to any one of claims 1, 6 to 12, wherein a resin layer is provided on one or both of the above surfaces. For example, the copper heat-radiating material according to item 28 of the patent application scope, wherein the resin layer contains a dielectric. A copper foil with a carrier has an intermediate layer and an ultra-thin copper layer in order on one or both sides of the carrier, and the ultra-thin copper layer is a copper heat-emitting material according to any one of claims 1 to 29 of the scope of patent application. For example, the copper foil with a carrier in the scope of the patent application No. 30, wherein one side of the carrier has the intermediate layer, the ultra-thin copper layer, and a roughened layer on the other side of the carrier. A connector using a copper heat radiating material according to any one of claims 1 to 29 of the scope of patent application. A terminal using a copper heat-dissipating material according to any one of claims 1 to 29 of the scope of patent application. A laminated body is manufactured in the following manner: a copper heat-generating material according to any one of the patent scopes 1 to 29 or a copper foil with a carrier, any adhesive layer, or Adhesive layer, and resin substrate or substrate or case or metal-processed member or electronic component or electronic device or liquid crystal panel or display or separator. A shielding material comprising a laminated body with the scope of application for item 34. A printed wiring board comprising a multilayer body with a scope of application for item 34. A metal-processed member using a copper heat-radiating material according to any one of the scope of claims 1 to 29 or a copper foil with a carrier having a scope of claims 30 or 31. An electronic device using a copper heat-radiating material according to any one of claims 1 to 29 or a copper foil with a carrier applying to items 30 or 31. A method for manufacturing a printed wiring board, comprising the following steps: preparing a copper foil with a carrier and an insulating substrate for applying for a patent scope item 30 or 31; laminating the copper foil with a carrier and an insulating substrate; and laminating the copper foil with a carrier After laminating with the insulating substrate, the metal-clad laminated board is formed through the step of peeling the carrier with the copper foil with the carrier, and then any one of the semi-additive method, subtractive method, partial additive method, or modified semi-additive method One way to form a circuit. A method for manufacturing a printed wiring board, comprising the steps of: forming a circuit on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier side of a copper foil with a carrier in the scope of patent application No. 30 or 31; Forming a resin layer on the ultra-thin copper layer side surface or the carrier-side surface of the copper foil with a carrier; forming a circuit on the resin layer; after forming a circuit on the resin layer, peeling off the carrier or the ultra-thin copper layer; and Because the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed, so that a circuit buried in the resin layer formed on the surface of the ultra-thin copper layer or the carrier-side surface is exposed.